EP0018473B1 - Procédé de préparation de bêta-alcoxyacrylonitriles, d'amino-3 acrylonitriles et d'esters de cyano-2 vinyle - Google Patents

Procédé de préparation de bêta-alcoxyacrylonitriles, d'amino-3 acrylonitriles et d'esters de cyano-2 vinyle Download PDF

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EP0018473B1
EP0018473B1 EP80101031A EP80101031A EP0018473B1 EP 0018473 B1 EP0018473 B1 EP 0018473B1 EP 80101031 A EP80101031 A EP 80101031A EP 80101031 A EP80101031 A EP 80101031A EP 0018473 B1 EP0018473 B1 EP 0018473B1
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meaning
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EP0018473A1 (fr
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Hermann Dr. Peeters
Uwe Dr. Prange
Wilhelm Dr. Vogt
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Huels Troisdorf AG
Dynamit Nobel AG
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Huels Troisdorf AG
Dynamit Nobel AG
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Priority claimed from DE19792912344 external-priority patent/DE2912344A1/de
Priority claimed from DE19792931228 external-priority patent/DE2931228A1/de
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/73—Unsubstituted amino or imino radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/14—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D295/145—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with the ring nitrogen atoms and the carbon atoms with three bonds to hetero atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings

Definitions

  • One aspect of the invention is the production of ⁇ -alkoxyacrylonitriles from metal salts of hydroxyacrylonitriles by reaction with halogen compounds.
  • chloroacetaldehyde is reacted with hydrocyanic acid to give ⁇ -hydroxy- ⁇ -chloropropionitrile, which in turn reacts further with acetic anhydride to give ⁇ -acetoxy- ⁇ -chloropropionitrile.
  • Pyrolysis of this compound leads to 33% ⁇ -chloroacrylonitrile. This reacts with alkali alcoholates to give ⁇ -alkoxyacrylonitrile (F. Scotti and E. J. Frazza, J. Org. Chem., 29, [1964] 1800).
  • ⁇ -alkoxyacrylonitriles can be prepared by reacting isoxazole with NaOH to give the sodium salt of ⁇ -hydroxyacrylonitrile and alkylating this compound in situ with diethyl sulfate or alkyl halides (GB-PS 8 06 235).
  • This synthesis requires several steps and expensive chemicals. In the absence of alkaline accelerators, low yields of 37.6% and low selectivity result from high proportions of C-alkyl compounds.
  • the slow course of the alkylation with dimethyl sulfate (US Pat. No. 2,375,185) is also disadvantageous.
  • the present invention is therefore based on the object of producing ⁇ -alkoxyacrylonitriles in a simple manner in high yield by a process which is technically and economically easy to implement.
  • the object is achieved in that an alkali or alkaline earth metal salt of ⁇ -hydroxyacrylonitriles of the general formula A is reacted with alkyl halides of the general formula B in the presence of a stabilizer and catalyst system to give a ⁇ -alkoxyacrylonitrile of the general formula C.
  • the substituents R and R ' are generally those which are inert towards the reactants. In the substituents R and R ', preference is given to those alkyl or alkenyl radicals having 1 to 6 carbon atoms. Among the radicals containing cyclic ring systems, mononuclear, ie monocyclic, strong, of the multinuclear the bicyclic are preferred.
  • the rings can directly via one or more atoms connected to one another or via one or more carbon or heteroatoms as a bridge.
  • the cycloaliphatic ring systems are preferably cycloalkane radicals, but one or more double bonds can also be present.
  • the heterocyclic radicals preferably contain nitrogen, optionally also oxygen or further heteroatoms.
  • the substituents of the ring systems which may be present are in themselves arbitrary, provided that these are inert in the reaction. Lower alkyl groups of 1 to 3 carbon atoms, chloro-methoxy, ethoxy or carbalkoxy groups are preferred.
  • alkali metal or alkaline earth metal salts of ⁇ -hydroxyacrylonitriles of the general formula A used for the preparation of the ⁇ -alkoxyacrylonitriles can be prepared according to the principle of Claisen's ester condensation from alkyl cyanides, formic acid esters and alkali metal or alkaline earth metal alcoholates.
  • a better method for the preparation of compounds of the general formula A is described in patent application P 27 53 322.8, in which alkyl cyanides are reacted with alkali or alkaline earth metal alcoholates in the presence of carbon monoxide. It is possible to use the compounds of the general formula A prepared according to this specification directly, without a further work-up step.
  • Na or K salts are preferably used as alkali or alkaline earth compounds of the formula A because of their easy accessibility.
  • Rb, Cs, Mg or Ca salts it is also possible to use.
  • the chlorine compounds are preferred as the halogen compound of the formula B.
  • Methyl chloride, ethyl chloride, propyl chloride, isopropyl chloride, n-butyl chloride, isobutyl chloride, sec-butyl chloride, tert-butyl chloride, 2-methoxyethyl chloride, cyclohexyl chloride, allyl chloride or benzyl chloride are particularly suitable.
  • the corresponding bromides or iodides can also be used, but have no advantages over the economically more interesting chlorides.
  • the halogen compounds are used in stoichiometric amounts or in excess, preferably in a ratio of 1 to 2 moles of halogen compound per mole of compound of the general formula A.
  • the excess halogen compound can be recycled.
  • a basic reaction compound of the alkali metals or alkaline earth metals is added to the reaction mixture, for example alkali metal hydroxides, bicarbonates or carbonates and alkaline earth metal oxides, bicarbonates or carbonates such as NaOH, KOH, NaHCO s , KHC0 3 , Na 2 C0 3 , K 2 C0 3 , MgO, CaO, MgC0 3 and CaC0 3 .
  • CaO is preferably used.
  • the basic reaction compound is used in a ratio of 0.05 to 1 equivalent per mole of compound of the general formula A.
  • cyclic radicals monocyclic radicals are preferred, of the aliphatic radicals those having 1 to 6 carbon atoms.
  • R 1 to R 4 are methyl, ethyl, propyl, butyl, octyl, cetyl, benzyl or phenyl.
  • anions such.
  • the preferred compound is tetra-n-butylammonium chloride, bromide or iodide.
  • the crown ethers which can be used instead of the quaternary ammonium salts are cyclic ethers of glycols, in which the numbers denote the number of glycol groups. For example, B. 15-crown-5, 18-crown-6, dibenzo-18-crown-6 and dicyclohexyl-18-crown-6.
  • the quaternary ammonium salt of the general formula E or the crown ether are used in catalytic amounts, based on compound A.
  • 10- 3 to 10- 1 mol of quaternary ammonium salt or crown ether is used per mole of compound A. Higher concentrations are possible, but economically inappropriate.
  • An iodine compound therefore a substance consisting of an iodide or a substance which forms iodine ions under reaction conditions, can also be added to the catalyst. As a result, the highest reaction rates and the best yields are generally achieved. So z. B. the quaternary ammonium salt of the general formula E can be added in the form of an iodide. It is also possible to add small amounts of the corresponding iodide to the alkyl halide of the general formula B. An inorganic salt with an iodide anion can also be used. As salts such. B. LiJ, NaJ, KJ, CuJ, ZnJ 2 or CoJ 2 can be used.
  • the iodine compound is added in a ratio of 10- 3 to 10- 1 mol per mol of compound of the general formula A.
  • Aprotic solvents are suitable as solvents.
  • So z. B. alkanes, benzene or toluene from the series of hydrocarbons can be used.
  • Ethers such as tetrahydrofuran, dimethoxyethane, di-, tri- or tetraglyme can be used.
  • Polar aprotic solvents such as hexamethylphosphoric triamide, dimethyl sulfoxide, dimethylformamide or acetonitrile are also good solvents for the reaction.
  • the solvent can be used in amounts of 0.5-21 per mole of compound of the general formula A. Larger amounts of solvent are possible, but have no advantages.
  • a range from 60 to 220 ° C. has proven to be favorable as the reaction temperature.
  • the reaction time is between 1 and 8 hours, complete conversion of compound A being achieved.
  • the reaction can be carried out under normal pressure, negative pressure or positive pressure up to 50 at. Higher pressures are possible, but not appropriate.
  • the pressure is preferably between normal pressure and the intrinsic pressure of the reactants.
  • the reaction can be carried out as follows: The starting material A is placed under an inert gas together with the basic inorganic salt, the quaternary ammonium salt and optionally the iodine compound in the solvent or dissolved in a reactor provided with a stirrer. The starting material B is then added, the reactor is closed and brought to the reaction temperature under autogenous pressure. After the reaction has ended, the mixture is cooled, the reactor is vented and the reaction mixture is removed. The solid is separated off by filtration or centrifugation and the end product C z. B. isolated by fractional distillation. ⁇ -alkoxyacrylonitriles are valuable starting materials for the production of heterocyclic compounds.
  • cytosine can be produced from ⁇ -ethoxyacrylonitrile and urea (GB-PS 806235). Furthermore, by reacting the end products C with hydrazine, 3-amino-4-alkyl-pyrazoles, with guanidine, 2,4-diamino-5-alkyl-pyrimidines with amidines, 2,5-dialkyl-4-aminopyrimidines can be prepared have a wide range of applications in the pharmaceutical and dye sector.
  • An alkali metal or alkaline earth metal salt of a ⁇ -hydroxyacrylonitrile, a basic salt, a quaternary ammonium salt of the general formula D and an iodine compound in an aprotic solvent are placed in a reactor with a stirring device at room temperature under an N 2 atmosphere. Depending on the physical state of the alkyl halide of the general formula B, this is also added or condensed.
  • the reactor is closed and heated to the reaction temperature under autogenous pressure. After the reaction has ended, the mixture is cooled and, in the case of alkyl halides B which are gaseous under normal conditions, the reactor is depressurized.
  • the reaction mixture is freed from solid constituents via a filter or a centrifuge and then fractionally distilled. Depending on the boiling point of the solvent used, this or the reaction product is obtained first.
  • the solvent can be used again for the reaction.
  • the reaction mixture consists of an E, Z isomer mixture.
  • the reaction mixture contains, in addition to the ⁇ -alkoxyacrylonitrile C, the ⁇ -alkyl-substituted compound D.
  • the reaction solution must be treated with mineral acids such as H 2 S0 4 , H 3 PO 5 or HCl advantageous, whereby the Z-configured isomer is converted into the more stable E isomer.
  • mineral acids such as H 2 S0 4 , H 3 PO 5 or HCl
  • Another aspect of the invention is the production of 3-aminoacrylonitriles from P-alkoxyacrylonitriles by reaction with amines.
  • 3-aminoacrylonitriles of the formula (1) were difficult or only accessible via costly starting materials, e.g. B. by reacting 3-chloroacrylonitrile with various amines (J. org. Chem. 29, (1964), 1800), dehydrogenation of 3-dimethylaminopropionitrile.
  • alkoxymethylene malodinitrile with aromatic amines according to DE-A 1 -2 800 764, DE-B-1 493 262 and DE-B 2 -1 807 634, it had to be assumed here that the two nitrile groups on represent a special case of the same carbon atom, this Favored reaction path.
  • substituents R 5 , R 6 and R has to be based, in particular when the process products are used as intermediates for further syntheses, on the substituent required in the end product. In general, the substituents should be inert to the reactants.
  • the rings can be connected to one another directly via one or more atoms or as a bridge via one or more carbon or heteroatoms.
  • the cycloaliphatic ring systems are preferably cycloalkane radicals, but one or more double bonds can also be present.
  • the heterocyclic radicals preferably contain nitrogen, optionally also oxygen or further heteroatoms.
  • the substituents of the ring systems which may be present are in themselves arbitrary, provided that these are inert in the reaction. Lower alkyl groups of 1 to 3 carbon atoms, chlorine and optionally alkoxy radicals are preferred.
  • radicals R insofar as these are alkyl or alkenyl radicals, short-chain ones with 1 to 6 C atoms are preferred.
  • radicals R containing cyclic ring systems are mononuclear, i.e. H. monocyclic very preferred, from the multinuclear to the bicyclic preferred.
  • the radicals R 5 and R 6 are H, lower aliphatic radicals having 1-6 C atoms, mononuclear aromatic or cycloaromatic radicals such as that of aniline or pyridine, and to the extent that R 5 and R 6 together form rings, the rings of morpholine and pyperidine or pyrrolidine preferred.
  • R 5 radicals are in particular the easily accessible lower alkyl radicals having 1 to 6 carbon atoms, and of these in particular methyl to propyl radicals are preferred.
  • the inventive method is advantageously carried out so that a 3-alkoxyacrylonitrile and an amine without solvent, in an inert polar organic solvent, for. B. an alcohol, acetonitrile, a polar aprotic solvent, e.g. B. dimethylformamide or dimethyl sulfoxide, etc., in a non-polar organic solvent, for. B. benzene, ether, n- or cyclo-paraffin, in water or suitable solvent mixtures thereof.
  • the amount of solvent that may be used is not critical, but too high dilutions will increase the reaction time.
  • the reaction can be carried out in the temperature range from -30 to about 250 ° C., preferably from + 10 ° C. to the boiling point of the reactants. In some cases, high yields are obtained in a short time even at low temperatures.
  • the reaction times depend on the temperature used and are generally about 0.5 to 5 hours.
  • the reaction can be carried out at normal pressure, negative pressure or positive pressure up to 50 bar. Higher pressures are possible, but not appropriate.
  • the pressure is preferably between normal pressure and the intrinsic pressure of the reactants.
  • the reaction can optionally be carried out by distilling off the alcohol R'OH formed in the course of the reaction, but this only gives advantages insofar as the reaction temperature is, for. B. can be increased if necessary when working under normal pressure.
  • the ratio of the molar equivalents of amine (E) to 3-alkoxyacrylonitrile (C) can be greater than, less than or equal to 1, depending on whether a largely complete conversion of amine (E) or 3-alkoxyacrylonitrile (C) is to be achieved; in general, a ratio of 4: 1 to 1: 4 is maintained, but high excesses of a reactant up to 1:10 can also be expedient.
  • reaction can be worked up simply by distillation, crystallization or extraction with a suitable solvent.
  • the reaction products are obtained in high yield and high purity.
  • reaction products are usually obtained as a cis / trans isomer mixture, the trans isomer generally predominating.
  • a second reactive amine can be added which catalyzes the reaction and does not occur in the end product.
  • NH 3 An example of these reactive amines is NH 3 , but other amines can also be used, e.g. B. morpholine or picoline.
  • the amount of the reactive amine can be one equivalent or more or less than one equivalent.
  • 3-aminoacrylonitriles of the formula (D) can be used to prepare various heterocycles, for.
  • Another aspect of the invention is the production of 3-amino-acrylonitriles from metal salts of hydroxy-acrylonitriles by reaction with amines.
  • the process according to the invention can be carried out in such a way that the metal salts of 3-hydroxyacrylonitriles of the formula (A) as a solid, suspension or dissolved to the suspension or solution of the amine of the formula (E) and the monobasic or polybasic inorganic or organic acid or to the Suspension or solution of the amine salt or to the suspension or solution of the amine of formula (E) and a salt of an inert amine is added.
  • the substances of the formula (A) and the amine of the formula (E) can also be introduced in dissolved or suspended form and the acid added, or the substances of the formula (A) can be introduced and the amine salt added.
  • Tertiary amines which do not take part in the reaction because of the lack of hydrogen atoms are added as inert amines.
  • the amine salt to be formed from the amine of the formula (E) and the acid can be prepared "in ' S itu" in the reaction solution from the corresponding amine and the acid by reaction in the ratio of their molar equivalents or used as an isolated salt.
  • Suitable acids are, for example: hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, but other common acids are also possible.
  • Amine salts are preferably the hydrochlorides or sulfates.
  • the ratio of the molar equivalents of the amines or amine salts to the substance of the formula (A) should be 1: 1 to 6: 1, advantageously 1: 1 to 3: 1.
  • the amount of acid or salt of an inert amine can be equivalent to the amine of formula (E), but an excess of acid is also possible.
  • reaction can be carried out in an inert polar or non-polar, neutral, basic or acidic organic solvent, in water or in suitable mixtures thereof.
  • Suitable solvents are for example: alcohols with 1 to 6 carbon atoms, acetonitrile, dimethylformamide, dimethyl sulfoxide, amines, e.g. B. an excess of the reacted amine or an inert tertiary amine, acetic acid, benzene, toluene, ether, but this selection is not meant to be limiting.
  • the amount of the solvent used is determined downwards by the good stirrability of the reaction mixture; there are no limits upwards, but dilutions which are too great result in lower yields and an extension of the reaction time.
  • the reaction can be carried out in the temperature range from -10 ° C to 200 ° C or above, preferably from 0 ° C to the boiling point of the solvent.
  • the reaction time depends on the reaction temperature used and is approximately between 1 h and 48 h.
  • the pressure should generally be between normal pressure and 50 bar. Higher pressures are possible, but not sensible.
  • reaction mixture is worked up, if appropriate after distilling off unreacted and / or salt formed in the reaction in the cold by concentrating the mother liquor and subsequent distillation or crystallization or by extraction with a suitable solvent from the aqueous reaction solution.
  • reaction products are generally obtained as a cis / trans isomer mixture, with the trans isomer predominating in most cases.
  • the last aspect of the invention is the production of 2-cyano-vinyl esters from metal salts of hydroxyacrylonitriles by reaction with acid halides or acid anhydrides.
  • the present process represents a considerable advantage over the known processes, since it proceeds in high yields when the reaction is simple and the starting products in the form of the acid chlorides (G) or acid anhydrides (H) and the 2-cyanovinyl alcoholates according to German patent application P 2 753 322.8 are easily accessible.
  • the process according to the invention is advantageously carried out in such a way that the acid halide of the formula (G) or the acid anhydride of the formula (H), optionally dissolved or suspended in an inert polar or non-polar solvent, to give the suspension of the cyanovinyl alcoholate of the formula (A) in one polar or non-polar solvent is added.
  • the acid halide of the formula (G) or the acid anhydride of the formula (H) optionally dissolved or suspended in an inert polar or non-polar solvent, to give the suspension of the cyanovinyl alcoholate of the formula (A) in one polar or non-polar solvent is added.
  • cooling to -40 to 20 ° C is advantageous.
  • the subsequent reaction takes place at temperatures from -40 to 100 ° C, preferably 1 -10 to 50 ° C.
  • Suitable inert solvents are e.g. B. benzene, toluene, ether, tetrahydrofuran, n- or cyclo-paraffins, acetone, acetonitrile, dimethylformamide or dimethyl sulfoxide.
  • the solvents must be anhydrous. The amount of the solvent used is limited by the stirrability of the reaction mixture. There are no upper limits, but dilutions that are too high result in yield losses and increase the reaction time. The reaction time depends on the reaction temperature and the nature of the reactants and is generally 1 to 24 hours.
  • the starting materials can be used in an equivalent quantitative ratio or with an excess of one component, the more accessible component, ie. H. the acid halide or the acid anhydride is used in excess.
  • the reaction mixture is worked up in a simple manner by filtering off the formed salt Me Hai n and possibly unreacted cyanovinyl alcoholate, distilling off the solvent and excess reagent and subsequent distillation or crystallization.
  • the 2-cyanovinyl esters of the formula (F) can be used to introduce 2-cyanovinyl groups, to prepare 2-cyanoethylcarboxylic acid esters by hydrogenating the double bond and as dyes in the presence of a suitable R 8 radical.
  • substituents R 8 and R of the substances produced according to the process are very different per se, depending on the constitution of the cyanovinyl esters used as intermediates and the end products produced therefrom according to the intended use. Accordingly, both are simply built Substituents R B and R as well as specially constructed substituents with a very specific structure and with very specific functional groups are possible.
  • substituents R 8 and R which are the aliphatic monocarboxylic acids having 1 to 6 C atoms, the aliphatic dicarboxylic acids having 1 to 6 C atoms, the unsubstituted aromatic mono- and dicarboxylic acids and their simple Substitution products, for example with methyl or chlorine substituents, correspond.
  • substituent R aliphatic substituents having 1 to 8 carbon atoms or substituted or unsubstituted benzyl radicals are also preferred for numerous cases.
  • 0.5 mol NaO-CH CH-CN, 1 mol C 2 H 5 ⁇ Cl, 500 ml acetonitrile, 1 g iodide promoter, 5 g tetra-n-butylammonium bromide and 0.5 mol CaO were used in each case.
  • Example 60 (Substance of Example 59)
  • Example 67 is repeated, but with ether instead of acetone as the solvent.

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Claims (20)

1. Procédé pour la préparation de P-alcoxyacrylonitriles de formule:
Figure imgb0057
dans laquelle R représente l'hydrogène, des radicaux alkyle, à chaîne droite ou ramifiée, ayant de 1 à 20 atomes de carbone, des radicaux -(CH2)n-CN, -(CH2)n-OR" ou -(CH2)n-CH(OR")2, à chaîne droite ou ramifiée, où n=de 0 à 5 et R" représente des radicaux alkyle ayant de 1 à 12 atomes de carbone, ou des radicaux ―(CH2)n+1―Cyc, avec Cyc représentant des systèmes isocycliques ou hétérocycliques, aromatiques ou cycloaliphatiques à un seul ou à plusieurs cycles, qui portent éventuellement des substituants sur les cycles, et n=de 0 à 5 et où R' représente des radicaux alkyle ou alcényle, à chaîne droite ou ramifiée, ayant de 1 à 12 atomes de carbone, des systèmes isocycliques ou hétérocycliques, aromatiques ou cycloaliphatiques à un ou plusieurs cycles qui portent éventuellement des substituants, ou ―(CH2)p―Cyc où Cyc a la signification précédente, des radicaux -(CH2)p-OR"' ou -(CH2-CH2-O)q-R"' avec p=de 1à 5 et q=de 1 à 4 et R"' représentant des radicaux alkyle, à chaîne droite ou ramifiée, ayant de 1 à 12 atomes de carbone, par réaction à température élevée de composés de formule:
Figure imgb0058
dans laquelle R a la signification indiquée ci-dessus et Me est un métal alcalin avec α=1 ou un métal alcalinoterreux avec α=2, avec un composé halogéné de formule R'-Hal (B) où R' a la signification indiquée ci-dessus et Hal désigne le chlore, le brome ou l'iode, lequel procédé est caractérisé en ce que la réaction a lieu en présence d'un composé à réaction basique de métaux alcalins ou alcalinoterreux.
2. Procédé selon la revendication 1, caractérisé en ce qu'on ajoute un sel d'ammonium quaternaire ou un éther-couronne à titre de catalyseur.
3. Procédé selon la revendication 2, caractérisé en ce qu'on utilise à titre de catalyseur une base ammonium quaternaire de formule générale (2):
Figure imgb0059
dans laquelle Ri, R2, R3 et R4 représent des radicaux cycloalkyle, aryle, alkylaryle, arylalkyle ou alkyle identiques ou différents, qui peuvent être linéaires ou ramifiés, ayant de 1 à 20 atomes de carbone et X est un anion monovalent.
4. Procédé selon la recendication 2, caractérisé en ce qu'à titre de catalyseur on utilise un éther-couronne.
5. Procédé selon l'une des revendications 3 ou 4, caractérisé en ce que le sel d'ammonium quaternaire ou l'éther-couronne est utilisé en des quantités de 10-3 à 10-1 mole par mole du composé (A).
6. Procédé selon l'une ou plusieurs des revendications 1 à 5, caractérisé en ce que comme autre catalyseur on ajoute un composé d'iode sous la forme d'un iodure ou d'un composé capable de former des ions d'iode.
7. Procédé selon la revendication 6, caractérisé en ce que le composé d'iode est ajouté en une proportion allant de 10-3 à 10-1 mole par mole du composé de formule générale A.
8. Procédé selon l'une ou plusieurs des revendications 1 à 7, caractérisé en ce qu'on utilise un milieu aprotique comme solvant.
9. Procédé selon l'une ou plusieurs des revendications 1 à 8, caractérisé en ce que la température de réaction est comprise entre 60 et 220° C de préférence entre 80 et 180° C.
10. Procédé pour la préparation de 3-aminoacrylonitriles de formule:
Figure imgb0060
dans laquelle R5 et R6 représentent l'hydrogène ou des radicaux alkyle, alcényle ou alcynyle, identiques ou différents, à chaîne droite ou ramifiée, ayant de 1 à 12 atomes de carbone, des radicaux -Cyc, -(CH2)n-Cyc où Cyc désigne des systèmes isocycliques, ou hétérocycliques, aromatiques ou cycloaliphatiques à un ou plusieurs cycles, qui peuvent porter éventuellement des substituants sur les cycles et n =de 0 à 5, le groupe -X-R7 où X représente des radicaux alkylène ou alcénylène, à chaîne droite ou ramifiée, ou cycliques ayant de 2 à 12 atomes de carbone, des radicaux -Cyc-, -(CH2)n-Cyc- ou (CH2)n―Cyc―(CH2)n où Cyc et n ont les significations ci-dessus et R7 =
Figure imgb0061
où R5 et R6 forment ensemble des radicaux alkylène ou alcényléne d'un cycle ayant de 3 à 6 membres, qui peut être éventuellement interrompu par un ou plusieurs hétéroatomes, et R représente l'hydrogène, des radicaux alkyle, à chaîne droite ou ramifiée, ou cycliques, ayant de 1 à 20 atomes de carbone, des radicaux -(CH2)n+1-CN, -(CH2)nOR", -(CH2)n-CH(OR")2 à chaîne droite ou ramifiée, où R" désigne des radicaux alkyle ayant de 1 à 12 atomes de carbone, ou ―(CH2)n+1―Cyc où Cyc et n ont les significations indiquées ci-dessus, mais auquel cas lorsque le radical est ―(CH2)n+1―CN, n ne doit pas être 5, lequel procédé est caractérisé en ce qu'on fait réagir un 3-alcoxyacrylonitrile ou un sel métallique de 3-hydroxyacrylonitriles avec de l'ammoniac ou une amine primaire ou secondaire, éventuellement en présence d'un mono- ou poly- acide minéral ou organique, avec des sels d'ammonium de ces acides.
11. Procédés pour la préparation de 3-aminoacrylonitriles selon la revendication 10, de formule:
Figure imgb0062
dans laquelle R5 et R6 représentent l'hydrogène, des radicaux alkyle, alcényle ou alcynyle, à chaîne droite ou ramifiée, ayant de 1 à 12 atomes de carbone, identiques ou différents, des groupes -Cyc, ―(CH2)n―Cyc, où Cyc représente un système isocyclique ou hétérocyclique, aromatique ou cycloaliphatique à un ou plusieurs cycles, qui peut éventuellement porter des substituants sur les cycles et n=de 0 à 5, le groupe -X-R7 où X représente des radicaux alkylène ou alcénylène à chaîne droite ou ramifiée, ou cycliques ayant de 2 à 12 atomes de carbone, des radicaux -Cyc-, ―(CH2)n―Cyc― ou -(CH2)n-Cyc-(CH2)n- où Cyc et n ont les mêmes significations que ci-dessus et R7 représente
Figure imgb0063
où R5 et R6 forment ensemble des radicaux alkylène ou alcénylène d'un cycle ayant de 3 à 6 membres, qui peut éventuellement être interrompu par un ou plusieurs hétéroatomes, et R est l'hydrogene, des radicaux alkyle à chaîne droite ou ramifiée, ou cycliques, ayant de 1 à 20 atomes de carbone, ou des radicaux à chaîne droite ou ramifiée de formule -(CH2)n+1-CN, -(CH2)nOR", -(CH2)n-CH(OR")2 où R" désigne des radicaux alkyle ayant de 1 à 12 atomes de carbone, ou -(CH2)n+1-Cyc où -Cyc et n ont les significations indiquées ci-dessus, mais auquel cas lorsque le radical est ―(CH2)n+1―CN n ne doit pas être 5, lequel procédé est caractérisé en ce qu'on fait réagir un 3-alcoxyacrylonitrile de formule:
Figure imgb0064
dans laquelle R a la signification indiquée ci-dessus et R' représente des radicaux alkyle ou alcényle à chaîne droite ou ramifiée ayant de 1 à 12 atomes de carbone, des systèmes isocycliques ou hétérocycliques, aromatiques ou cycloaliphatiques à un ou plusiers cycles, qui peuvent éventuellement porter des substituants, ou -(CH2)p-Cyc, Cyc ayant la signification ci-dessus, les radicaux ―(CH2)p-OR" ou -(CH2-CH2-O)q-R''' où p=de 1 à 5 et q=de 1 à 4 et R''' représente des radicaux alkyle, à chaîne droite ou ramifiée, ayant de 1 à 12 atomes de carbone, avec des amines de formule
Figure imgb0065
dans laquelle R5 et R6 ont les significations ci-dessus.
12. Procédé selon la revendication 11, caractérisé en ce que la réaction est conduite entre - 30 et 250° C, de préférence entre 0° C et le point d'ébullition des réactifs.
13. Procédé selon l'une des revendications 11 ou 12, caractérisé en ce que la réaction est conduite en présence d'une amine supplémentaire qui catalyse la réaction.
14. Procédé pour la préparation de 3-aminoacrylonitriles selon la revendication 10, de formule
Figure imgb0066
dans laquelle R5 et R6 représentent l'hydrogène, des radicaux alkyle, alcényle ou alcynyle, à chaîne droite ou ramifiée, ayant de 1 à 12 atomes de carbone, identiques ou différents, des radicaux -Cyc, ―(CH2)n―Cyc où Cyc désigne des systèmes isocycliques, ou hétérocycliques, aromatiques ou cycloaliphatiques à un ou plusieurs cycles, qui peuvent éventuellement porter des substituants sur les cycles et n = de 0 à 5, le groupe -X-R7 où X désigne des radicaux alkylène ou alcénylène ayant de 2 à 12 atomes de carbone, -Cyc, ―(CH2)n―Cyc― ou -(CH2)n-Cyc-(CH2)n- où Cyc et n ont les significations ci-dessus et R7 est
Figure imgb0067
ou R5 et R6 forment ensemble des radicaux alkylène ou alcényléne d'un cycle ayant de 3 à 6 membres qui est éventuellement interrompu par un ou plusieurs hétéroatomes, et R représente l'hydrogène, des radicaux alkyle, à chaîne droite ou ramifiée, ou cycliques ayant de 1 à 20 atomes de carbone, des radicaux ―(CH2)n+1―CN, ―(CH2)n―OR', ―(CH2)n―CH(OR)2 à chaîne droite ou ramifiée, où R'désigne des radicaux alkyle ayant de 1 à 12 atomes de carbone ou (CH2)n+1―Cyc où Cyc et n ont les significations ci-dessus, mais auquel cas lorsque le radical est ―(CH2)n+1―CN, n de doit pas être 5, lequel procédé est caractérisé en ce qu'on fait réagir un composé de formule
Figure imgb0068
dans laquelle R a la signification ci-dessus et Me est un métal alcalin avec a = 1 ou un métal alcalino- terreux avec a = 2, avec une amine de formule
Figure imgb0069
dans laquelle R5 et R6 ont la signification indiquée ci-dessus, en présence d'un mono- ou poly- acide minéral ou organique ou en présence d'un sel d'une amine inerte ou avec un sel d'amine d'un des acides mentionnés et d'une amine de formule (E).
15. Procédé selon la revendication 14, caractérisé en ce que la réaction est conduite à une température comprise entre -10 et 200°C, de préférence entre 0°C et la température d'ébullition des réactifs.
16. Procédé selon l'une des revendications 14 ou 15, caractérisé en ce que le rapport des équivalents molaires de l'amine de formule (E) ou du sel d'amine à la substance de formule (A) est de 1 : 1 à 6 : 1, de préférence de 1 : 1 à 3 : 1.
17. Procédé pour la préparation d'esters de 2-cyanovinyle de formule générale
Figure imgb0070
dans laquelle n est 1 ou 2 et RB représente des radicaux alkyle, alkylène, alcényle ou alcénylène à chaîne droite ou ramifiée, ayant de 1 à 12 atomes de carbone, des systèmes isocycliques ou hétérocycliques avec une structure à un ou plusieurs cycles ou (CH2)m―Cyc, où Cyc est un noyau isocyclique ou hétérocyclique avec une structure à un ou plusieurs cycles, qui peut éventuellement porter des substituants sur les cycles et m =de 0 à 5, et R représente l'hydrogène, des radicaux alkyle à chaîne droite ou ramifiée, ou cycliques, ayant de 1à 20 atomes des carbone, des radicaux -(CH2)p-CN, -(CH2)p-COOR"', -CH2)p-NH2, -(CH2)p-OR"', -(CH2)p+1,-Cyc à chaîne droite ou ramifiée où Cyc désigne un système isocyclique ou hétérocyclique avec une structure à un ou plusieurs cycles ou un cycle aromatique ou hétéroaromatique avec une structure à un ou plusieurs cycles, qui peut éventuellement porter des substituants sur les cycles, R''' représente des radicaux alkyle ayant de 1 à 12 atomes de carbone ou des restes de phénols monovalents et p=de 0 à 5, lequel procédé est caractérisé en ce qu'on fait réagir un composé de formule:
Figure imgb0071
dans laquelle R a la même signification que dans la formule (F) et Me est un métal alcalin avec a = 1 ou un métal alcalino-terreux avec a = 2, avec un halogénure d'acide de formule
Figure imgb0072
dans laquelle n et R' ont les significations indiquées pour la formule (F) et Hal désigne le chlore ou le brome, ou avec un anhydride d'acide de formule
Figure imgb0073
dans laquelle R8 a la même signification que dans la formule (F).
18. Procédé selon la revendication 17, caractérisé en ce que la réaction a lieu dans un solvant organique, inerte, polaire ou non polaire.
19. Procédé selon l'une des revendications 17 et 18, caractérisé en ce que la réaction est conduite à une température comprise entre - 40 et 100° C, de préférence entre - 10 et 50° C.
20. Procédé selon l'une quelconque des revendications 17 à 19, caractérisé en ce que l'halogénure (G) ou l'anhydride d'acide (H) est amené à réagir avec l'alcool cyanovinylique (A) dans un rapport équivalent ou en excès.
EP80101031A 1979-03-29 1980-03-03 Procédé de préparation de bêta-alcoxyacrylonitriles, d'amino-3 acrylonitriles et d'esters de cyano-2 vinyle Expired EP0018473B1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
DE19792912345 DE2912345A1 (de) 1979-03-29 1979-03-29 Verfahren zur herstellung von beta -alkoxyacrylnitrilen
DE2912344 1979-03-29
DE2912345 1979-03-29
DE2912343 1979-03-29
DE19792912343 DE2912343A1 (de) 1979-03-29 1979-03-29 Verfahren zur herstellung von 3-aminoacrylnitrilen aus metallsalzen von 3-hydroxyacrylnitrilen
DE19792912344 DE2912344A1 (de) 1979-03-29 1979-03-29 Verfahren zur herstellung von 3-aminoacrylnitrilen
DE19792931228 DE2931228A1 (de) 1979-08-01 1979-08-01 Verfahren zur herstellung von 2-cyanovinylestern
DE2931228 1979-08-01

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DE3206878A1 (de) * 1982-02-26 1983-09-15 Dynamit Nobel Ag, 5210 Troisdorf Verfahren zur herstellung von 3-alkoxi-acrylnitrilen
DE3211679A1 (de) * 1982-03-30 1983-10-06 Dynamit Nobel Ag Verfahren zur herstellung von acetalen und enolaethern aus acyloxymethylenverbindungen
EP0174910B1 (fr) * 1984-09-12 1990-04-04 Ciba-Geigy Ag Procédé pour la préparation de dérivés de 4-dérivés de 4-phényl-pyrrole
DE4223013A1 (de) * 1992-07-13 1994-01-20 Bayer Ag Verfahren zur Herstellung von 2,5-disubstituierten Pyridinen
US5354343A (en) * 1992-08-31 1994-10-11 Shell Oil Company Gasoline composition
ATE177140T1 (de) * 1993-12-13 1999-03-15 Shell Int Research Benzinzusammensetzung

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AT148477B (de) * 1933-09-21 1937-01-25 Kohlentechnik Gmbh Verfahren zur Darstellung von Aminofettsäurenitrilen.
US2375185A (en) * 1940-10-10 1945-05-08 Roche Products Ltd Manufacture of methoxymethylene malonitrile
GB806235A (en) * 1957-04-26 1958-12-23 Kay Fries Chemicals Inc Preparation of cytosine and intermediates
CH443256A (de) * 1964-06-23 1967-09-15 Takeda Chemical Industries Ltd Verfahren zur Herstellung von Aminomethylenmalononitril
US3551573A (en) * 1967-11-08 1970-12-29 Monsanto Co Insecticidal composition and method containing anilinomethylene malonitriles
JPS4916846B1 (fr) * 1970-02-24 1974-04-25
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IT7819092A0 (it) * 1977-01-10 1978-01-06 Ciba Geigy Prodotti antielmintici, procedimento per la loro preparazione e loro impiego.
EP0001760B1 (fr) * 1977-10-27 1981-01-07 BASF Aktiengesellschaft Alpha-aminométhylène-bêta-formylaminopropionitrile, procédé pour sa préparation et son utilisation dans la préparation de 2-méthyl-4-amino-5-formylaminométhylpyrimidine

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